Ester-ethers of bis-phenols



Patented Oct. 3, 1944 I 2,359,622 ESTER-ETHERS OF BIS-PHENOLS Gerald H. Coleman and Bartholdt C. Hadler, Midland, Mich, and Robert W. Sam. Wilmington,

Del., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing.

Original application November 7,

1940, Serial No. 364,688. Divided and this application August 28, 1943, Serial No. 500,428

8 Claims.

This invention concerns certain new esterethers of bis-phenols and a method of making the same. By a bis-phenol is meant a dihydric phenolic compound formed by condensing an aldehyde or a ketone with two molecular equivalents of a monohydric phenol of the benzene series.

The bis-phenols of which the new ester-ethers are derivatives have the general formula:

are preferably employed per mole of the bisphenol or its alkali metal salt, but the halohydriu may be employed in smaller or larger proportion if desired. The reaction is usually carried out at temperatures between 60 and 120 C., but it may in some instances be carried out at lower or higher temperatures. The reaction is usually complete after from 1 to 6 hours of heating at temperatures within the range just given The product may be separated by conventional purification procedure, e. g. by washing thereacted mixture with water to extract alkali metal halide, e. g. sodium chloride, therefrom and then heating under vacuum to distill any lower boilwherein R and X have the above meanings and R is an alkylene radical, may be prepared by the direct reaction of an alkylene oxide, e. g. ethylene oxide, propylene oxide,-or butylene oxide, etc.. with a bis-phenol. The reaction may be carried out by heating the bis-phenol, preferably with stirring, at a reaction temperature between 125 and 170 C. and passing the olefine oxide into the heated bis-phenol until the desired amount of olefine oxide has been absorbed. If desired, a catalyst such as sodium or potassium hydroxide, or a basic amine, or acids such as sulphuric or phosphoric acid, etc., may be employed in small proportion to promote the reaction, but the use of a catalyst is not required.- The product may be separated by distilling low-boiling ingredients, e. g. unreacted olefine oxide and bisphenol, from the mixture.

However, di-hydroxyalkyl ethers of bis-phenols having the above general formula are preferably prepared by reacting an olefine halohydrin, e. g. ethylene chlorohydrin, ethylene bromohydrin, propylene chlorohydrin, propylene bromohydrin, or a butylene chlorohydrin, etc.; with an alkali metal salt of a bis-phenol. The reaction is carried out by heating a sodium or potassium salt of a bis-phenol, or a mixture of the bis-phenol and sufficient sodium or potassium hydroxide to form such salt, and an olefine halohydrin to a reaction temperature in the presence of water, alcohol, or other suitable liquid medium. Approximately 2 moles of the olefine halohydrin mg ingredients from the product. The hydroxyalkyl ethers of bis-phenols thus prepared vary at room temperature from extremely viscous liquids to noncrystalline resinous solids to solids which may be crystallized.

The ester-ethers (l. e. acyloxy-alkyl ethers) of bis-phenols are prepared by esterifying the above di-hydroxyalkyl ethers of the bis-phenols, They have the general formula:

wherein Y represents an acyl radical, e. g. an acetyl, propionyl, butryl, crotonyl, levulinyl, benzoyl, naphthoyl, or cinnamoyl radical, etc., and R, R, and X have the meanings hereinbefore given. The esterification is carried out in accordance with usual esterification procedure, e. g. by heating a mixture of the hydroxy-alkyl ether of a bis-phenol and an organic carboxylic acid under reflux in the presence of an esterificat'ion catalyst, such as hydrochloric acid, sulphuric acid, or benzene sulphonic acid, etc. Water may advantageously be distilled from the mixture as it is formed. The removal of water during the reaction may be facilitated by carrying the es terification out in the presence of a volatile water-immiscible solvent, such as benzene, ethylene chloride, carbon tetrachloride, etc., which will distill together with the water at temperatures below the boiling point of water alone. After completing the reaction, the ester product is separated as usual, e. g. by distillation. The acyloxy-alkyl ethers of bis-phenols so obtained are usually extremely viscous liquids or noncrystalline resinous solids at room temperature, although they may in some instances be obtained in crystalline form, They are highly efiective as plasticizing agents and are particularly useful as agents for plasticizing thermoplastic resins so as to increase their moldability without unduly softening them at room temperature.

The following examples describe a number of ways in which the principle of the invention has Example 1 Example 4 A mixture of 0.3 gram mole of 2.2-di-(4-hydroxy-phenyDbutane, 0.675 gram mole of sodium hydroxide and 200 cc. of Water was heated A mixture of 1 gram mole of 2.2-di-(4-hydroxypheny1-) propane, 2.25 gram moles of so- 2 3??? g z fig m i g g'ggg dium hydroxide,. 400 cc. of water and 300 cc. of i 1 g inuies 6 3 n t ethyl alcohol was heated under reflux at temper- 1 w m ontm'ued f mg a gz 2 3 atures between 800 and and gram liours The iir duct was t erf separat d as in i Fthylene 93: 2 was gg z i i 10 Example 2. There was obtained 0.264 gram mole lininufiiirfiiidatnai 3 $5.... at. 51.151? of Z-Z-di 4-bemmyemyrphenyl1mm the mixture was washed with water and the low- In the form an g a g i at boiling ingredients were distilled from the prod- 23;. tempera e pro as t e oruct under vacuum. The residual material was recrystallized from benzene. There was obtained 0.94 gram mole of 2.2-di-(4-beta-hydroxy-ethno-cmonroO-e-go-cmcnron oxy-phenyl) propane as a nearly white crystal- E line solid having a melting point or approximate- 1y 112C. The product has the formula:

. CH3 1 Example 5 7 I nowmcflroggowmcnrofl A mixture of 0.3 gram mole of 2.2-di-(3-meth- 'yl-4-hydroxyphenyl)propane, 0.675 gram mole of sodium hydroxide, and 200 cc. of water was heatp Z ed under reflux to approximately 90 C., and

A mixture of 1 grams of (4 hydmxy 0.675 gram mole of ethylene chlorohydrin was phenyl propane, 236 grams of sodium hydrox 7 added thereto in about 15 minutes. Heating at ide, 250 cc. of water and 1200 cc. of 95 per cent t mperatures etween 90 and 95 C. was conconcentrated ethyl alcohol was heated to about tmued for an additional 3.5 hours after which the 70 C. and an aqueous solution of 970 grams of Product w separated as Example There propylene chlomhydrin and 1010 grams f water was obtained 0.17 gram mole of 2.2-di-(3-methwas added over a period of 1 hour and 10 min- 314'beta'hydmxyethoxy'phenyl)ppane in the tea The temperature varied from to 0 Q form of an extremely viscous reddish-brown liqduring the addition. The mixture stood over d- The-pmduct has the night, after which it was treated with an addi- CH: tional 20 grams of sodium hydroxide and heated 30011201124) @OWCHICHHE to a temperature of 8283 C. for 4.5 hours. The I l mixture was then cooled to approximately room temperature, whereupon it separated into layers. 40 E l 6 The organiclayer was separated from the aqueramp e ous alcohol layer and was washed consecutively A'mixture of 0.399 gram mole of 1.1-di-(4-hywith a 20 per cent sodium hydroxide solution and droxy-phenyl-) cyclohexane, 0.675 mole of sowater and then dried. There were obtained 314 dium hydroxide, 300 cc. of water and 25 cc. of grams of product in the form of an extremely ethyl alcohol was heated under reflux to about viscous brown liquid which wa insoluble in aque- C- a d g a m of y e o oous sodium hydroxide solutions. The product hydrin was added gr u y in ut 35 inconsisted substantially of 2.2-di-(4-hydroxyutes. The mixture was heated with stirring at propoxy-phenyl-) propane, having the formula: temperatures between 90 and 93 C.-for anad- CH: ditional 3.5 hours. The mixture was then diluted with 500 cc. of ethylene chloride, and the O- solution was washed successively with dilute aqueous sodium hydroxide solution and'water.

" The ethylene chloride and other low-boiling ini Example 3 gredients were then distilled from the product,

A mixture of 03 grammole of 1 '4 the distillation being completed under vacuum.

' he 1 t 0575 gram m of ar. There was'obtained 0.332 gram mole of 1.1-di- .um' hydroxide, and 200 cc. of water was heated e a-hydroxyethoxy phenyl cyclohexane undeleflux at temperature between 35 and in the form of a cream-colored non-crystalline 5 C" and 75 gram mole of ethylene l 00 solid which was quite brittle at room temperwas added gradually during a period f ature. The product has the formula:

0.5. hour. Heating was continued for an additi'onal 3.5-hours, after which the mixture was HO'CHZCHPOQCOO-CHZCHPOH washed with water and the low-boiling ingredicuts were distilled from the product under vac- H1 .IH, uum. There was obtained 0.268 gram mole of 4 H, on, v 1.1-di-(4-hydroxy-ethoxy-phenyl)butane in the C form of a soft noncrystalline solid. The product has the formula: Example 7 The 2.2-di (4-beta-hydroxyethoxy-phenyl-) pro- O? O W pane obtained in Example 1 was esterified by heat- I on, ing a mixture of 0.15 gram mole of the same, 0.3

H, gram mole of cinnamic acid, 5 grams of benzene- CH sulphonic acid, and 150 cc. of benzene under reflux at temperatures between and C. for 4 hours 15 minutes. During the heating, a'mixuum. There was obtained 0.42 gram mole of ture oi benzene and the waterformed by the 2.2-di-(4 -(beta-levulinyloxyethoxy- )phenyl-)- reaction was distilled from the mixture. The propane in the form 01 an amber-colored viscous reacted mixture was neutralized with aqueous liquid having a specific gravity of approximately sodium hydroxide, washed with water, and sub- 5 1.166 at 25" C. 'The product has the formula: jected to distillation under vacuum for the pure on pose of removing lower-boiling materials from I 6 the ester product. The latter was then recrys- 0 O tallized from di-isopropyl ether. There was ob--- H, e on. on. tained 0.5 gram mole or 2.2-di-(4-(beta-cin- 1o 5. namoyloxy ethoxy )phenyl )propane as a J nearly white crystalline solid having a melting A: I point 01 l05-106.5 c. The product has the n. in. formula: 4 a

CH1 =0 {i=0 mc-oO-cGo-cm en. 1 Hzt l' CH: CH: Example 10 I A mixture of 0.172 gram mole of 2.2-di-(4-betahydroxy-ethoxy-phenyl)-butane, 0.346 gram H mole of glacial acetic acid, 5 grams of benzene II II sulphonic acid, and 250 cc. of benzene was heated under reflux at temperatures between 78 and 84 C. for 2 hours, water and benzene being dis- Emmple 8 tilled therefrom during the heating. The ester A mixture of 0.5 gram mole of 2.2-di-(4-betaproduct was then separated as in Example '7. hydroxy-ethoxy-phenyl-)propane, 1 gram mole There was obtained 0.138 gram mole of 2.2-diof crotonic acid, 5 grams of benzene sulphonic (4-(beta-acetyloxy-ethoxy-phenyhpropanc in acid, and 400 cc. of benzene was heated under the form of a viscous yellow liquid which distilled reflux at temperatures between 83 and 86 C. at temperatures between 240 and 245 C. at 1 for 15 hours, 15 minutes, a mixture of benzene millimeter absolute pressure and had a specific and water formed by the esterification being disgravity approximately 1.144. at 25 C. The prodtilled ofi during the heating. The reacted mixnot has the formula:

0 CH3 0 mo-r'i-o-cmcm-oOrig-Om-cmom-o--cm ture was washed successively with a dilute Example 11 aqueous sodium hydroxide solution and water ixture of 0.1 gram mole of cyclohexylideneafter which the product was separated by distil t ano1) 0.2 gram mole ximatel 0.5 Egg g g g jgfizi igg f f of benzolc acid, 5 grams of benzene sulphomc acid ethoxy phenyl )propane as a viscous yellow and 250 cc. of benzene was heated under reflux liquid distilling at temperatures between 225 and at temperatures between 82 and 90 C. for 7 275 C. at 1 millimeter absolute pressure and havhours 45 tes, While distilling benzene and ing a specific gravity of approximately 1.132 at. water formed by the reaction therefrom. The 25 C. with respect to water at the same temperester product was then separated as in Example ature. The product has the formula: 7. There was obtained 0.04 gram mole of 1.1-di- CH: O

Example 9 i-beta -benzoxy ethoxy-) phenyl-) cyclohexane A mixture of 0.5 gram mole of 2.2-di-(beta-hyas a soft amber-colored resin. The product has droxy-eth0xy-phenyDpr0pane, 1 gram mole of the formula:.

levulin'ic acid, 5 grams of benzene sulphonic acid Example 12 a 350 cc. of benzene was heated under reflux ai iemperatures between 82 and 90 C. for 2.5 70 A mixture of 137 grams of the hours, water and benzene being distilled theredroxy-propoxy-phenywpropane obtained i from during the heating The mixture was t ample 2, grams of glacial acetic acid, 250 cc. washed with an aqueous sodium hydroxide soluof benzene. nd 5. grams of benzene sulphonic tion and water after which low-boiling ingreacid was heated at temperatures which varied dients were distilled from the product under vac- 7 from 86 to 92 C. for 3 hours, while continuously distilling off a mixture of benzene and the w'ater 1. An ester-ether having the general formula:

formed by the reaction and separating benzene from the distillate and returning it to the reac- R tion mixture. The mixture. was then cooled,

washed with 250 cc. of a saturated aqueous sodi- 6 um bicarbonate solution and then with approximately 1 liter of water. The mixture was then distilled, first at atmospheric pressure to remove, the benzene and thereafter under vacuum to represen S member of the group consisting of separate the ester product. There was obtained 10 ogen and alkyl radicals, and Y represents 135 grams of a highly viscous, slightly yellow an acyl radlcal of carPoxylic acidliquid ester-ether which distilled at 235-245 c. An ester-ether havmg t e general formula: at 1 millimeter pressure with some decomposition and which had a specific gravity of about 1.108 PO-R O G at 25 C. with respect to water at 4 C. The wherein R represents an alkyndene radical, ester-ether Product is represents an alkylene radical, and Y represents wherein R represents a radical selected from the class consisting of alkylidene and cycloalkylidene radicals, R represents an alkylene radical, X

. oxy-)phenyl-)propane, having the formula: an acyl radical of a carboxylic amt 3. An ester-ether having the general formula:

CH: N

wherein R represents an alkylene radicafand Y Other hydroxy-ethers an}? esterfiethers 61; 1215- represents an acyl radical of a carboxync acid. phenols may be prepared y sim ar proce ure. An 1 th h h For instance, an alkali metal salt of the bisester 8 er g: t e mg phenol, 2.2-di(3-ethyl-4-hydroxy-phenyI-)pro- E J} pane, may be reacted with an oleflne halohydrin, Q --0- e. g. ethylene chlorohydrin, propylene chloro- (EH1 hydrin, or butylene chlorohydrin, to form a corwherein R represents an alkylene radical.

responding hydrox'y-alkyl ether of the bis-phenol, i, e. a hydroxy-ethyl ether, a hydroxy-propyl propane, having the formula:-

ether, or a hydroxy-butyl ether of the bis-phenol, 0 CH 0 and the hydroxy-ether may be reacted with a II J carboxylic acid, e. g. acetic acid, propionic acid, O H' or benzoic acid, etc., to form a corresponding 33H:

ester-e her of he bis-pheno 6. An ester-ether having the general formula: This application is a division of our copending CH application, Serial No. 364,688, filed November 7, I j 1940 and which has now matured into Patent 40 (B Number 2,331,265.

Other modes of applying the principle of the wherein Y is an acyl radical of a ,carboxylic acid.

invention may be employed instead of those '7. 2.2-di-(4-(beta-crotonyloxy-ethoxy-)phenexplained, changes being made as regards the y1-propane,-having the formula:

t CH: o HaC--CH= CHCO-CH:CH:-OOOOCHICH:-OgCH=CHCHa (1311:

method or compounds herein disclosed, pro- 8. 2.2-di-(4-(beta-levulinyloxy-ethoxy-) phenvided the steps or compounds stated by any of yl-)propane, having the formula:

CH; o 1 0 C HsC CHzCHsC-O-C H1CH:0('3O-OCH:CHr0 CHlCHl CHl JJH: the following claims or the equivalent of such GERALD H. COLEMAN. stated steps or compounds be employed. BARTHOLDT C. HADLER.

We therefore particularly point out and dis- ROBERT W. SAPP. tinctly claim as our invention:

5. 2.2 di (4 (acetyloxy-propoxy-) phenyb) 

